Effects of calcium compounds on the carbothermic reduction of vanadium titanomagnetite concentrate

Effects of calcium compounds on the carbothermic reduction of vanadium titanomagnetite concentrate(VTC) were investigated. It was found that calcium compounds had great effects on the metallization rate of the reduction product, the order of the metallization rate of reduction product being CaCO_3 no additive CaSO_4 CaCl_2, which indicated that the addition of CaCO_3 was more conducive to promoting the reduction of iron than other calcium compounds. Gas analysis showed that there were mainly two processes in the carbothermic reduction of VTC, a solid–solid and a solid–gas reaction. The concentrations of CO and CO_2 were highest when CaCO_3 was added, while that in a roasting system decreased the most when CaCl_2 was added. X-ray diffraction(XRD) analysis showed that calcium compounds could change the reduction process of ilmenite in VTC. The phase compositions of the reduction products were changed from metallic iron(Fe) and anosovite(FeTi_2O_5) to metallic iron(Fe) and perovekite(CaTiO_3) when calcium compounds were added. Additionally, CaSO_4 and CaCl_2 could significantly promote the growth of metallic iron particles, though the existence of Fe-bearing Mg_2TiO_4 in reduction products was not conducive to the reduction of iron. The formation of FeS would further hinder the reduction of iron after adding CaSO_4.     

添加CaCO3后碳热还原钒钛磁铁矿精矿过程中钛酸钙的形成

The formation of calcium titanate in the carbothermic reduction of vanadium titanomagnetite concentrate (VTC) by adding CaCO₃ was investigated. Thermodynamic analysis was employed to show the feasibility of calcium titanate formation by the reaction of ilmenite and CaCO₃ in a reductive atmosphere, where ilmenite is more easily reduced by CO or carbon in the presence of CaCO₃. The effects of CaCO₃ dosage and reduction temperature on the phase transformation and metallization degree were also investigated in an actual roasting test. Appropriate increase of CaCO₃ dosages and reduction temperatures were found to be conducive to the formation of calcium titanate, and the optimum conditions were a CaCO₃ dosage of 18wt% and a reduction temperature of 1400°C. Additionally, scanning electron microscopy–energy dispersive spectrometry (SEM–EDS) analysis shows that calcium titanate produced via the carbothermic reduction of VTC by CaCO₃ addition was of higher purity with particle size approximately 50 μm. Hence, the separation of calcium titanate and metallic iron will be the focus in the future study.     

Formation of calcium titanate in the carbothermic reduction of vanadium titanomagnetite concentrate by adding CaCO_3

The formation of calcium titanate in the carbothermic reduction of vanadium titanomagnetite concentrate(VTC) by adding CaCO_3 was investigated. Thermodynamic analysis was employed to show the feasibility of calcium titanate formation by the reaction of ilmenite and Ca CO_3 in a reductive atmosphere, where ilmenite is more easily reduced by CO or carbon in the presence of CaCO_3. The effects of CaCO_3 dosage and reduction temperature on the phase transformation and metallization degree were also investigated in an actual roasting test. Appropriate increase of CaCO_3 dosages and reduction temperatures were found to be conducive to the formation of calcium titanate, and the optimum conditions were a CaCO_3 dosage of 18 wt% and a reduction temperature of 1400°C. Additionally, scanning electron microscopy–energy dispersive spectrometry(SEM–EDS) analysis shows that calcium titanate produced via the carbothermic reduction of VTC by CaCO_3 addition was of higher purity with particle size approximately 50 μm. Hence, the separation of calcium titanate and metallic iron will be the focus in the future study.     

Phase transformation and reduction kinetics during the hydrogen reduction of ilmenite concentrate

The reduction of ilmenite concentrate by hydrogen gas was investigated in the temperature range of 500 to 1200℃. The microstructure and phase transition of the reduction products were studied by X-ray diffraction (XRD), scanning electron microscopy (SEM), and optical microscopy (OM). It was found that the weight loss and iron metallization rate increased with the increase of reduction temperature and reaction time. The iron metallization rate could reach 87.5% when the sample was reduced at 1150℃ for 80 min. The final phase constituents mainly consist of Fe, M₃O₅ solid solution phase (M=Mg, Ti, and Fe), and few titanium oxide. Microstructure analysis shows that the surfaces of the reduction products have many holes and cracks and the reactions take place from the exterior of the grain to its interior. The kinetics of reduction indicates that the rate-controlling step is diffusion process control with the activation energy of 89 kJ·mol-1.     

Carbothermic reduction of vanadium titanomagnetite with the assistance of sodium carbonate

The carbothermic reduction of vanadium titanomagnetite concentrate (VTC) with the assistance of Na₂CO₃ was conducted in an argon atmosphere between 1073 and 1473 K.X-ray diffraction and scanning electron microscopy were used to investigate the phase transformations during the reaction.By investigating the reaction between VTC and Na₂CO₃,it was concluded that molten Na₂CO₃ broke the structure of titanomagnetite by combining with th...     

微波预处理对复杂铜矿磨矿及浮选动力学的影响

The effect of CaCO₃, Na₂CO₃, and CaF₂ on the reduction roasting and magnetic separation of high-phosphorus iron ore containing phosphorus in the form of Fe₃PO₇ and apatite was investigated. The results revealed that Na₂CO₃ had the most significant effect on iron recovery and dephosphorization, followed by CaCO₃, the effect of CaF₂ was negligible. The mechanisms of CaCO₃, Na₂CO₃, and CaF₂ were investigated using X-ray diffraction (XRD), scanning electron microscopy and energy dispersive spectrometry (SEM–EDS). Without additives, Fe₃PO₇ was reduced to elemental phosphorus and formed an iron–phosphorus alloy with metallic iron. The addition of CaCO₃ reacted with Fe₃PO₇ to generate an enormous amount of Ca₃(PO₄)₂ and promoted the reduction of iron oxides. However, the growth of iron particles was inhibited. With the addition of Na₂CO₃, the phosphorus in Fe₃PO₇ migrated to nepheline and Na₂CO₃ improved the reduction of iron oxides and growth of iron particles. Therefore, the recovery of iron and the separation of iron and phosphorus were the best. In contrast, CaF₂ reacted with Fe₃PO₇ to form fine Ca₃(PO₄)₂ particles scattered around the iron particles, making the separation of iron and phosphorus difficult.     

Application of a water cooling treatment and its effect on coal-based reduction of high-chromium vanadium and titanium iron ore

A water cooling treatment was applied in the coal-based reduction of high-chromium vanadium and titanium (V–Ti–Cr) iron ore from the Hongge region of Panzhihua, China. Its effects on the metallization ratio (η), S removal ratio (R_S), and P removal ratio (R_P) were studied and analyzed on the basis of chemical composition determined via inductively coupled plasma optical emission spectroscopy. The metallic iron particle size and the element distribution of Fe, V, Cr, and Ti in a reduced briquette after water cooling treatment at 1350°C were determined and observed via scanning electron microscopy. The results show that the water cooling treatment improved the η, R_S, and R_P in the coal-based reduction of V–Ti–Cr iron ore compared to those obtained with a furnace cooling treatment. Meanwhile, the particle size of metallic iron obtained via the water cooling treatment was smaller than that of metallic iron obtained via the furnace cooling treatment; however, the particle size reached 70 μm at 1350°C, which is substantially larger than the minimum particle size required (20 μm) for magnetic separation. Therefore, the water cooling treatment described in this work is a good method for improving the quality of metallic iron in coal-based reduction and it could be applied in the coal-based reduction of V–Ti–Cr iron ore followed by magnetic separation.     

Recovery of iron from high phosphorus oolitic iron ore using coal-based reduction followed by magnetic separation

Oolitic iron ore is one of the most important iron resources. This paper reports the recovery of iron from high phosphorus oolitic iron ore using coal-based reduction and magnetic separation. The influences of reduction temperature, reduction time, C/O mole ratio, and CaO content on the metallization degree and iron recovery were investigated in detail. Experimental results show that reduced products with the metallization degree of 95.82% could be produced under the optimal conditions (i.e., reduction temperature, 1250℃; reduction time, 50 min; C/O mole ratio, 2.0; and CaO content, 10wt%). The magnetic concentrate containing 89.63wt% Fe with the iron recovery of 96.21% was obtained. According to the mineralogical and morphologic analysis, the iron minerals had been reduced and iron was mainly enriched into the metallic iron phase embedded in the slag matrix in the form of spherical particles. Apatite was also reduced to phosphorus, which partially migrated into the metallic iron phase.     

CaCO<Subscript>3</Subscript> film synthesis from ladle furnace slag: morphological change,new material properties,and Ca extraction efficiency

A rapidly air-cooled ladle furnace slag (RA-LFS), which is a type of steelmaking slag discharged from a steel mill, was used to synthesize CaCO₃ film. The CaCO₃ film with 35 cm2 of surface area was synthesized under atmospheric conditions, and the surface morphology of the CaCO₃ films was changed by using additives (CaCl₂ and ethylene glycol). Especially, the addition of CaCl₂ changed the surface morphology of CaCO₃ film with pore and induced new material properties, such as water adsorption. The (012) face of CaCO₃ film (calcite) was rapidly decreased by the addition of CaCl₂. The major components of RA-LFS were calcium (type of CaO, 53.9wt%) and aluminum (type of Al₂O₃, 37.9wt%), and the major crystal phases of RA-LFS were C₃S, C₁₂A₇, and C₃A. The calcium extraction efficiency of RA-LFS was significantly increased after the CaCO₃ film synthesis. The material properties (hardness and elastic modulus) and the thermal characteristics of the CaCO₃ films were analyzed by nano-indentation and thermogravimetry-differential thermal analysis. The synthesized CaCO₃ films from RA-LFS and Ca(OH)₂ (reagent) showed similarities in terms of their material properties and the decomposition temperature.     

Effect of Cr2O3 addition on oxidation induration and reduction swelling behavior of chromium-bearing vanadium titanomagnetite pellets with simulated coke oven gas

The oxidation induration and reduction swelling behavior of chromium-bearing vanadium titanomagnetite pellets (CVTP) with Cr₂O₃ addition were studied, and the reduction swelling index (RSI) and compressive strength (CS) of the reduced CVTP with simulated coke oven gas (COG) injection were investigated. The results showed that the CS of the CVTP decreases and the porosity of the CVTP increases with increasing amount of Cr₂O₃ added. The Cr₂O₃ mainly exists in the form of (Cr, Fe)₂O₃ solid solution in the CVTP and as Fe-Cr in the reduced CVTP. The CS of the reduced CVTP increases and the RSI of the reduced CVTP decreases with increasing amount of Cr₂O₃ added. The limited aggregation and diffusion of metallic iron contribute to the formation of dense lamellar crystals, which leads to the slight decrease for reduction swelling behavior of reduced CVTP. This work provides a theoretical and technical basis for the utilization of CVTP and other Cr-bearing ores such as chromite with COG recycling technology.     

Generation process of FeS and its inhibition mechanism on iron mineral reduction in selective direct reduction of laterite nickel ore

Numerous studies have demonstrated that Na₂SO₄ can significantly inhibit the reduction of iron oxide in the selective reduction process of laterite nickel ore. FeS generated in the process plays an important role in selective reduction, but the generation process of FeS and its inhibition mechanism on iron reduction are not clear. To figure this out, X-ray diffraction and scanning electron microscopy analyses were conducted to study the roasted ore. The results show that when Na₂SO₄ is added in the roasting, the FeO content in the roasted ore increases accompanied by the emergence of FeS phase. Further analysis indicates that Na₂S formed by the reaction of Na₂SO₄ with CO reacts with SiO₂ at the FeO surface to generate FeS and Na₂Si₂O₅. As a result, a thin film forms on the surface of FeO, hindering the contact between reducing gas and FeO. Therefore, the reduction of iron is depressed, and the FeO content in the roasted ore increases.     

烧结铁矿中FeO含量对其在富氢高炉中还原行为的影响

Japan started the national project “COURSE 50” for CO₂ reduction in the 2000s. This project aimed to establish novel technologies to reduce CO₂ emissions with partially utilization of hydrogen in blast furnace-based ironmaking by 30% by around 2030 and use it for practical applications by 2050. The idea is that instead of coke, hydrogen is used as the reducing agent, leading to lower fossil fuel consumption in the process. It has been reported that the reduction behavior of hematite, magnetite, calcium ferrite, and slag in the sinter is different, and it is also considerably influenced by the sinter morphology. This study aimed to investigate the reduction behavior of sinters in hydrogen enriched blast furnace with different mineral morphologies in CO–CO₂–H₂ mixed gas. As an experimental sample, two sinter samples with significantly different hematite and magnetite ratios were prepared to compare their reduction behaviors. The reduction of wustite to iron was carried out at 1000, 900, and 800°C in a CO–CO₂–H₂ atmosphere for the mineral morphology-controlled sinter, and the following findings were obtained. The reduction rate of smaller amount of FeO led to faster increase of the reduction rate curve at the initial stage of reduction. Macro-observations of reduced samples showed that the reaction proceeded from the outer periphery of the sample toward the inside, and a reaction interface was observed where reduced iron and wustite coexisted. Micro-observations revealed three layers, namely, wustite single phase in the center zone of the sample, iron single phase in the outer periphery zone of the sample, and iron oxide-derived wustite FeO and iron, or calcium ferrite-derived wustite 'FeO' and iron in the reaction interface zone. A two-interface unreacted core model was successfully applied for the kinetic analysis of the reduction reaction, and obtained temperature dependent expressions of the chemical reaction coefficients from each mineral phases.     

Migration behaviors and kinetics of phosphorus during coal-based reduction of high-phosphorus oolitic iron ore

To understand the migration mechanisms of phosphorus (P) during coal-based reduction, a high-phosphorus oolitic iron ore was reduced by coal under various experimental conditions. The migration characteristics and kinetics of P were investigated by a field-emission electron probe microanalyzer (FE-EPMA) and using the basic principle of solid phase mass transfer, respectively. Experimental results showed that the P transferred from the slag to the metallic phase during reduction, and the migration process could be divided into three stages:phosphorus diffusing from the slag to the metallic interface, the formation of Fe-P compounds at the slag-metal interface and P diffusing from the slag-metal interface to the metallic interior. The reduction time and temperature significantly influenced the phosphorus content of the metallic and slag phases. The P content of the metallic phase increased with increasing reduction time and temperature, while that of the slag phase gradually decreased. The P diffusion constant and activation energy were determined and a migration kinetics model of P in coal-based reduction was proposed. P diffusion in the metallic phase was the controlling step of the P migration.     

Thermodynamic analysis of the carbothermic reduction of a high-phosphorus oolitic iron ore by FactSage

A thermodynamic analysis of the carbothermic reduction of high-phosphorus oolitic iron ore (HPOIO) was conducted by the FactSage thermochemical software. The effects of temperature, C/O ratio, additive types, and dosages both on the reduction of fluorapatite and the formation of liquid slag were studied. The results show that the minimum thermodynamic reduction temperature of fluorapatite by carbon decreases to about 850°C, which is mainly ascribed to the presence of SiO₂, Al₂O₃, and Fe. The reduction rate of fluorapatite increases and the amount of liquid slag decreases with the rise of C/O ratio. The reduction of fluorapatite is hindered by the addition of CaO and Na₂CO₃, thereby allowing the selective reduction of iron oxides upon controlled C/O ratio. The thermodynamic results obtain in the present work are in good agreement with the experimental results available in the literatures.     

Gas-based reduction of vanadium titano-magnetite concentrate: behavior and mechanisms

The reduction of vanadium titano-magnetite pellets by H₂-CO at temperatures from 850 to 1050℃ was investigated in this paper. The influences of pre-oxidation treatment, reduction temperature, and V_H2/(V_H2 + V_CO) on the metallization degree were studied. The results showed that pre-oxidation played a substantial role in the reduction of vanadium titano-magnetite pellets. During the reduction process, the metallization degree increased with increasing temperature and increasing V_H2/(V_H2 + V_CO). The phase transformation of pre-oxidized vanadium titano-magnetite pellets during the reduction process under an H₂ atmosphere and a CO atmosphere was discussed, and the reduced samples were analyzed by scanning electron microscopy (SEM) in conjunction with back scatter electron (BSE) imaging. The results show that the difference in thermodynamic reducing ability between H₂ and CO is not the only factor that leads to differences in the reduction results obtained using different atmospheres. Some of Fe_3-xTi_xO₄ cannot be reduced under a CO atmosphere because of the densification of particles' structure and because of the enrichment of Mg in unreacted cores. By contrast, a loose structure of particles was obtained when the pellets were reduced under an H₂ atmosphere and this structure decreased the resistance to gas diffusion. Moreover, the phenomenon of Mg enrichment in unreacted cores disappeared during H₂ reduction. Both the lower resistance to gas diffusion and the lack of Mg enrichment facilitated the reduction of vanadium titano-magnetite.     

Comprehensive recovery of lead,zinc, and iron from hazardous jarosite residues using direct reduction followed by magnetic separation

Lead, zinc, and iron were recovered from jarosite residues using direct reduction followed by magnetic separation. The influence of the coal dosage, reduction temperature, and reduction time on the volatilization rates of lead and zinc and the metallization rate of iron were investigated. The results show that the volatilization rates of lead and zinc were 96.97% and 99.89%, respectively, and the iron metallization rate was 91.97% under the optimal reduction roasting conditions of a coal dosage of 25.0wt% and reduction roasting at 1250℃ for 60 min. The magnetic concentrate with an iron content of 90.59wt% and an iron recovery rate of 50.87% was obtained under the optimum conditions in which 96.56% of the reduction product particles were smaller than 37 μm and the magnetic field strength was 24 kA/m. Therefore, the results of this study demonstrate that recovering valuable metals such as lead, zinc, and iron from jarosite residues is feasible using the developed approach.     

Comprehensive recovery of lead,zinc, and iron from hazardous jarosite residues using direct reduction followed by magnetic separation

Lead, zinc, and iron were recovered from jarosite residues using direct reduction followed by magnetic separation. The influence of the coal dosage, reduction temperature, and reduction time on the volatilization rates of lead and zinc and the metallization rate of iron were investigated. The results show that the volatilization rates of lead and zinc were 96.97% and 99.89%, respectively, and the iron metallization rate was 91.97% under the optimal reduction roasting conditions of a coal dosage of 25.0 wt% and reduction roasting at 1250°C for 60 min. The magnetic concentrate with an iron content of 90.59 wt% and an iron recovery rate of 50.87% was obtained under the optimum conditions in which 96.56% of the reduction product particles were smaller than 37 μm and the magnetic field strength was 24 k A/m. Therefore, the results of this study demonstrate that recovering valuable metals such as lead, zinc, and iron from jarosite residues is feasible using the developed approach.     

Effects of Na<Subscript>2</Subscript>SO<Subscript>4</Subscript> on iron and nickel reduction in a high-iron and low-nickel laterite ore

This study investigates the reactions of Na₂SO₄ and its effects on iron and nickel reduction in the roasting of a high-iron and low-nickel laterite ore through gas composition, X-ray diffraction, and scanning electron microscope analyses. Results showed that a reduction reaction of Na₂SO₄ to SO₂ was performed with roasting up to 600℃. However, no clear influence on iron and nickel reductions appeared, because only a small amount of Na₂SO₄ reacted to produce SO₂. Na₂SO₄ reacted completely at 1000℃, mainly producing troilite and nepheline, which remarkably improves selective reduction of nickel. Furthermore, the production of low-melting-point minerals, including troilite and nepheline, accelerated nickel reduction and delayed iron reduction, which is attributed to the concurrent production of magnesium magnetite, whose structure is more stable than the structure of magnetite. Reduction reactions of Na₂SO₄ resulted in weakening of the reduction atmosphere, and the main product of Na₂SO₄ changed and delayed the reduction of iron. Eventually, iron metallization was effectively controlled during laterite ore reduction roasting, leading to iron mainly being found in wustite and high iron-containing olivine.     

Recovery of iron and calcium aluminate slag from high-ferrous bauxite by high-temperature reduction and smelting process

A high-temperature reduction and smelting process was used to recover iron and calcium aluminate slag from high-ferrous bauxite. The effects of w(CaO)/w(SiO₂) ratio, anthracite ratio, and reduction temperature and time on the recovery and size of iron nuggets and on the Al₂O₃ grade of the calcium aluminate slag were investigated through thermodynamic calculations and experiments. The optimized process conditions were the bauxite/anthracite/slaked lime weight ratio of 100:16.17:59.37, reduction temperature of 1450°C and reduction time of 20 min. Under these conditions, high-quality iron nuggets and calcium aluminate slag were obtained. The largest size and the highest recovery rate of iron nuggets were 11.42 mm and 92.79wt%, respectively. The calcium aluminate slag mainly comprised Ca₂SiO₄ and Ca₁₂Al₁₄O₃₃, with small amounts of FeAl₂O₄, CaAl₂O₄, and Ca₂Al₂SiO₇.     

Carbothermic reduction behaviors of Ti-Nb-bearing Fe concentrate from Bayan Obo ore in China

To support the development of technology to utilize low-grade Ti-Nb-bearing Fe concentrate, the reduction of the concentrate by coal was systematically investigated in the present paper. A liquid phase formed when the Ti-Nb-bearing Fe concentrate/coal composite pellet was reduced at temperatures greater than 1100℃. The addition of CaCO₃ improved the reduction rate when the slag basicity was less than 1.0 and inhibited the formation of the liquid phase. Mechanical milling obviously increased the metallization degree compared with that of the standard pellet when reduced under the same conditions. Evolution of the mineral phase composition and microstructure of the reduced Ti-Nb-bearing Fe concentrate/coal composite pellet at 1100℃ were analyzed by X-ray diffraction and scanning electron microscopy-energy-dispersive spectroscopy. The volume shrinkage value of the reduced Ti-Nb-bearing Fe concentrate/coal composite pellet with a basicity of 1.0 was approximately 35.2% when the pellet was reduced at 1100℃ for 20 min, which enhanced the external heat transfer to the lower layers when reduced in a practical rotary hearth furnace. The present work provides key parameters and mechanism understanding for the development of carbothermic reduction technology of a Ti-Nb-bearing Fe concentrate incorporated in a pyrometallurgical utilization flow sheet.